KR20060069860A - Phyllosilicate and thermoplastic resin composition containing the same - Google Patents

Abstract

A phyllosilicate characterized by being capable of undergoing 50 to 100% ion exchange with organic onium ions based on the ion-exchange ability and having a specific surface area of 2. 5 to 100 m2/g; a resin composition comprising a thermoplastic resin and the phyllosilicate, characterized in that the content of the phyllosilicate is 0.01 to 20 parts by weight, in terms of inorganic ash amount, per 100 parts by weight of the thermoplastic resin and that the number of sheets of the phyllosilicate in the thermoplastic resin is 2 to 8 on the average; and a film comprising the resin composition.

Description

Layered silicate and thermoplastic resin composition containing it {PHYLLOSILICATE AND THERMOPLASTIC RESIN COMPOSITION CONTAINING THE SAME}

The present invention relates to an ion exchanged layered silicate, a production method thereof, a thermoplastic resin composition comprising the layered silicate and a thermoplastic resin, and a film comprising the resin composition. More specifically, the present invention relates to an ion exchanged layered silicate that is preferably dispersible in a thermoplastic resin composition, a thermoplastic resin composition in which the layered silicate is appropriately dispersed in a thermoplastic resin, and a film made of the resin composition.

Thermoplastic resins including polyesters are used in various applications by utilizing their excellent mechanical properties, moldability, heat resistance, weather resistance, light resistance, chemical resistance, and the like. However, with recent advances in technology, more advanced properties have been required for resins depending on the applications used. As one of the technologies which satisfy | fill these required characteristics, the composition which disperse | distributed the layered compound in the nanoscale to a thermoplastic resin, what is called nanocomposite, has attracted attention in recent years. By forming nanocomposites, various characteristics such as high heat resistance, high elasticity, flame retardation, and gas barrier performance have been improved. Industry Survey, 2000). In order to form a nanocomposite, it is necessary to disperse a layered compound on a nanoscale, and various methods are tried. For example, when producing a composite material of polyester in which a layered compound is dispersed at a single layer level, it is disclosed to use an organic cation having a functional group reactive with a polyester monomer in an organic modified body of the layered compound ( Japanese Patent Laid-Open No. 9-48908). Moreover, there exists a description of the polyester resin composition which melt-mixed the layered silicate of 15-35 micrometers of interlayer distances to a polyester resin, and disperse | distributing uniformly, maintaining the layer structure of 5-20 layers. number). Japanese Laid-Open Patent Publication No. 2003-327851 also describes a method of producing a layered inorganic crystal-polymer composite by freeze drying the swellable layered inorganic crystals and then impregnating the molten polymer. However, especially in nanocomposites using polyester, it is difficult to disperse to the same extent as polyamide, and further improvement in dispersibility is desired.

Detailed description of the invention

Disclosure of the Invention

An object of this invention is to provide the ion-exchange layered silicate which can be preferably disperse | distributed to a thermoplastic resin composition, its manufacturing method, the thermoplastic resin composition which consists of this layered silicate and a thermoplastic resin, and the film which consists of this resin composition.

Still other objects and advantages of the present invention will become apparent from the following description.

According to the present invention, the above objects and advantages of the present invention are achieved by a layered silicate characterized in that the organic onium ion is ion exchanged by 50 to 100% relative to the ion exchange capacity, and the specific surface area is 2.5 to 100 m 2 / g. .

Moreover, according to this invention, the said objective and advantage of this invention are the resin composition which consists of a thermoplastic resin and said layered silicate secondly, and content of layered silicate is 0.01 to inorganic ash content with respect to 100 weight part of thermoplastic resins. It is achieved by the resin composition which is 20 parts by weight.

 Brief description of the drawings

1 is an electron micrograph of the resin composition of Example 7. FIG.

2 is an electron micrograph of the resin composition of Comparative Example 2. FIG.

Preferred Embodiments of the Invention

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

The layered silicate used in the present invention is preferably a 2: 1 type in which an octahedral sheet structure containing Al, Mg, Li, or the like is sandwiched between two SiO4 tetrahedral sheet structures, and specifically, saponite and hector. Swelling properties such as smectite clay minerals such as light, fluorine hectorite, montmorillonite, bedelite and stevensite, Li type fluorine teniolite, Na type tenorite, Na type silicon fluoride mica and Li type silicon fluoride mica Synthetic mica, vermiculite, fluorine vermiculite, halosite, swellable mica and the like. Moreover, these may be natural or synthesize | combined. Among them, smectite clay minerals such as montmorillonite, hectorite, Li-type fluorine teniolite, Na-type tetrasilicon fluoride mica and the like can be preferably used from the viewpoint of cation exchange capacity and the like.

In the layered silicon salt of the present invention, the layered silicon salt is ion exchanged by 50 to 100% with respect to ion exchange capacity by organic onium ions.

As organic onium ion, quaternary onium ions, such as phosphonium and ammonium, or heteroaromatic ion are preferable. It is more preferable that organic onium ion is represented by following formula (1).

Wherein M is a nitrogen atom or a person atom. R ₁ , R ₂ , R ₃ And R ₄ are each independently a hydrocarbon group containing 1 to 30 carbon atoms or a hetero atom, and optionally R ₁ , R ₂ , or R _3. And R ₄ may form a ring)

Regarding the organic onium ion represented by the formula (1), M is a phosphonium ion as the person atom, M is a nitrogen atom, and any R ₁ , R ₂ , R ₃ And R ₄ forms a ring to be a heteroaromatic ion.

As a C1-C30 hydrocarbon group, an alkyl group and an aromatic group are mentioned. As an alkyl group, a C1-C18 alkyl group is preferable, and methyl, ethyl, n-propyl, n-butyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, and n-octadecyl can be illustrated preferably. Moreover, as an aromatic group, a phenyl group, a biphenyl group, benzyl group, a tosyl group, etc. can be illustrated preferably. Moreover, a preferable example is a phenyl group, a biphenyl group, a benzyl group, a tosyl group, etc. as these aromatic groups. Moreover, these aromatic groups may have substituents, such as methyl, ethyl, fluorine, and chlorine, which do not affect their thermal stability.

Specific examples of quaternary ammonium in which M is a nitrogen atom include tetramethylammonium, tetraethylammonium, tetrabutylammonium, triethylbenzylammonium, tetraoctylammonium, trimethyldecylammonium, trimethyldodecylammonium, trimethylhexadecylammonium and trimethyloctadecylammonium. And various tetraalkylammoniums such as tributylmethylammonium, tributyldodecylammonium, tributyloctadecylammonium, trioctylethylammonium, tributylhexadecylammonium, methyltriphenylammonium and ethyltriphenylammonium are mentioned as preferred ones. .

Specific examples of the organic phosphonium in which M is a member include tetraethylphosphonium, triethylbenzylphosphonium, tetrabutylphosphonium, tetraoctylphosphonium, trimethyldecylphosphonium, trimethyldodecylphosphonium, trimethylhexadecylphosphonium, Trimethyloctadecylphosphonium, tributylmethylphosphonium, tributyldodecylphosphonium, tributyloctadecylphosphonium, trioctylethylphosphonium, tributylhexadecylphosphonium, methyltriphenylphosphonium, ethyltriphenylphosphonium , Diphenyl dioctyl phosphonium, triphenyl octadecyl phosphonium, tetraphenyl phosphonium, tributyl allyl phosphonium, etc. are mentioned.

In addition, in the case of the hydrocarbon group in which the formula (1) contains a hetero atom, the above-mentioned hydrocarbon group having 1 to 30 carbon atoms R ₁ , R ₂ , R ₃ And at least a part of R ₄ is at least one member selected from the group consisting of a C1-C30 hydroxy substituted hydrocarbon group, an alkoxy substituted hydrocarbon group, a phenoxy substituted hydrocarbon group, and an imide substituted hydrocarbon group. Do.

Examples of the hydrocarbon group having a substituent containing a hetero atom are listed below (wherein a and b are each independently an integer of 1 or more and 29 or less and an integer such that carbon number in the substituent is 30 or less). )

Hydroxy substituted hydrocarbon group

Alkoxy Substituted Hydrocarbon Groups:

Phenoxy Substituted Hydrocarbon Groups:

Imide Substituted Hydrocarbon Groups:

In addition, R ₁ , R ₂ , R ₃ And R ₄ When a polyvalent ring is formed into a heteroaromatic ion, pyridine derivatives such as pyridine, methylpyridine, ethylpyridine, dimethylpyridine, hydroxypyridine, dimethylaminopyridine, imidazole, methylimidazole, dimethylimidazole, ethyl And organic onium ions composed of pyrazole derivatives such as imidazole derivatives such as imidazole and benzimidazole, pyrazole, methylpyrazole, dimethylpyrazole, ethylpyrazole and benzpyrazole.

Especially, as an imidazole derivative, N-methyl imidazolinium, N-ethyl imidazolinium, N-hexyl imidazolinium, N-octylimidazolinium, N-dodecyl imidazolinium, N- Examples of alkyl substituted imidazolinium such as hexadecyl imidazolinium, and a hydrocarbon group having a substituent containing a hetero atom as described above, illustrate N-substituted imidazolinium and their alkyl substituents. Can be.

The organic onium ions described above can be used alone or in combination. As organic onium ion, it is preferable to have a phosphonium or an imidazolinium structure from the heat resistant surface of layered silicate. As a more preferable organic onium ion, specifically, alkyl phosphonium, such as tetrabutyl phosphonium, tetraoctyl phosphonium, tributyl dodecyl phosphonium, tributyl hexadecyl phosphonium, N-methyl imidazolinium, N- Alkyl-substituted imidazoliniums, such as ethyl imidazolinium, N-hexyl imidazolinium, N-octyl imidazolinium, N-dodecyl imidazolinium, and N-hexadecyl imidazolinium, and an alkyl group The following onium can be illustrated by which a part of is substituted by the imide substituted hydrocarbon group.

(Wherein a is an integer of 1 or more and 29 or less).

In the substituent as described above, the suitable a value may be changed depending on the type or combination of the layered silicate and the thermoplastic resin to be dispersed.

 The layered silicate of the present invention is ion exchanged by 50 to 100% with respect to the cation exchange capacity of the layered silicate by such organic onium ions.

 The cation exchange capacity of the layered silicate can be measured by a conventionally known method, but as the ion exchange capacity of the layered silicate used in the present invention, a layer of about 0.2 to 3 meq / g can be preferably used among the layered silicates described above. The cation exchange capacity of 0.2 meq / g or more is advantageous in terms of dispersibility in order to increase the introduction rate of organic onium ions. In addition, the introduction of organic onium ions is easier and preferable at 3 meq / g or less. It is more preferable that cation exchange capacity is 0.8-1.5 meq / g.

The cation exchange rate of the layered silicate of the present invention is 50 to 100%, and the cation exchange rate of 50% or more is advantageous in terms of dispersibility in order to increase the introduction rate of organic onium ions to the layered silicate. Since the cation exchange rate is 100% or less, since the biion of the onium compound used for a raw material does not exist, it is advantageous at the point of thermal stability. As cation exchange rate, it is more preferable that it is 55 to 99%, and it is still more preferable that it is 60 to 99%.

The exchange rate of such a cation can be computed by following formula (2).

Cation exchange rate (%) = {Wf / (1-Wf)} / (Morg / Msi) × 100 (2)

     (Wf is the weight loss rate by differential thermal balance of layered silicate measured from 120 ° C to 800 ° C at a heating rate of 20 ° C / min, Morg is the molecular weight of the phosphonium ion, Msi is 1 in the cation portion of the layered silicate) The molecular weight per charge in the cation portion of the layered silicate is the value calculated from the inverse of the cation exchange capacity (unit: eq / g) of the layered silicate (109 meq for Kunipia F). / 100 g)

In addition, the presence or absence of the onium ion which does not participate in cation exchange with respect to a layered silicate is confirmed by measuring the presence or absence of the biion of the onium compound used as a raw material by a conventionally well-known method, such as fluorescence X-rays and atomic absorption spectrometry. It is possible to do

Moreover, it is preferable that the temperature at the time of 5 weight% weight reduction when the layered silicate of this invention is measured by differential thermal balance at the temperature increase rate of 20 degree-C / min in nitrogen atmosphere is 310 degreeC or more. When the temperature at the time of 5 wt% weight reduction is lower than 310 ° C., when the melt is kneaded with the thermoplastic resin, the decomposition is large, and when the resin properties are deteriorated, such as reaggregation of the layered silicate or generation of decomposition gas. There is. From this point of view, the temperature at the time of 5 weight% weight reduction is so preferable that it is high, but considering the structure of the organic onium ion which gives favorable dispersibility as layered silicate of this invention, Preferably it is 330 degreeC or more, More preferably, Preferably it is 340 degreeC or more, More preferably, it is 350 degreeC or more.

The layered silicate of the present invention is characterized by having a specific surface area of 2.5 to 10 m 2 / g. The specific surface area can be obtained by the BET method using nitrogen. By setting the specific surface area to 2.5 m 2 / g or more, the efficiency of dispersion upon melt kneading with the resin is improved, and a thermoplastic resin of the layered silicate and the thermoplastic resin uniformly dispersed can be obtained. On the contrary, when the specific surface area exceeds 100 m 2 / g, the particles become too large because the specific surface area is too large, so that the bulk density becomes high and the handling as powder becomes difficult, which is not preferable. As a specific surface area, 4-80000 m <2> / g is more preferable, and 5-50 m <2> / g is more preferable.

     As a method of exchanging the cation of the layered silicate with organic onium ions, a conventionally known method is possible. Specifically, a layered silicate is dispersed in a polar solvent such as water, ethanol or methanol, and an organic onium ion is added thereto or a solution containing an organic onium ion is mentioned.

The preferable concentration of the layered silicate in the layered silicate dispersion is 0.1 to 5% by weight. When the concentration is lower than 0.1 wt%, the total amount of the solution is too large, which is undesirable in handling. When it exceeds 5 weight%, since the viscosity of the dispersion of layered silicate becomes too high, cation exchange rate falls and it is unpreferable. As concentration of layered silicate, 0.5-4.5 weight% is more preferable, and 1-4 weight% is more preferable.

As temperature at the time of reaction, what is necessary is just to have a viscosity low enough for stirring the dispersion liquid of layered silicate, for example, in the case of water, it is preferable to perform cation exchange reaction at about 20-80 degreeC.

     The layered silicate of the present invention can be produced by lyophilizing the layered silicate exchanged with organic onium ions in this way using a medium having a melting point of -20 ° C or more and less than 100 ° C. It is preferable that the medium used for freeze drying has melting | fusing point -20 degreeC or more. If the melting point of the medium is lower than -20 ° C, the freezing temperature of the medium is too low, so the freezing temperature is lowered and the removal efficiency of the medium may be lowered.

As a preferable medium used for freeze drying, water, benzene, cyclohexane, cyclohexanone, benzyl alcohol, P-dioxane, cresol, P-xylene, acetic acid, cyclohexanol and the like can be exemplified.

The medium used for freeze drying may be the same as that used for the dispersion of the cation exchange reaction, or a medium in which the layered silicate after the cation exchange reaction is well dispersed may be used. In particular, in the case of a medium in which the layered silicate is well dispersed, the specific surface area can be considerably increased because freeze drying can be performed while the silicate layer of the layered silicate is separated.

Freeze-drying is performed by freezing the dispersion liquid which consists of layered silicate and a medium, and removes a medium under reduced pressure. The concentration of the layered silicate in the dispersion at the time of freeze drying is usually about 0.5 to 70% by weight, and when the solvent is a good solvent, the concentration range may be about 0.1 to 50% by weight. If the concentration of the layered silicate in the dispersion is too high, gelation is undesirable. Preferably from 0.5% to 30%, most preferably from 1% to 10% by weight. In addition, the kind of freeze dryer is not specifically limited, Commercially available freeze dryer can be used preferably.

Here, good dispersion refers to a form in which the layered silicate is peeled and swelled in a good dispersion medium, which is subjected to TEM measurement by a method according to Shomers (Document C. and Clay Minerals, Vo 1.26, 135-138 (1978)). It can be determined by a method of measuring the distance between layers, such as a method of measuring a wide angle, or X-ray measurement. As a degree of favorable dispersion, it is preferable that the interlayer distance of the layered silicate calculated | required by X-ray measurement in a favorable dispersion medium is at least 1 nm or more.

By performing lyophilization in this manner, the layered silicate of the present invention can be produced.

The resin composition of this invention is a resin composition which consists of a thermoplastic resin and the above-mentioned layered silicate, The content of a layered silicate is 0.01-20 weight part as inorganic ash with respect to 100 weight part of thermoplastic resins, The layer form in a thermoplastic resin Silicate is an average layer number of 2-8 layers, It is a resin composition characterized by the above-mentioned.

An inorganic component is a residue at the time of performing the thermogravimetric analysis to 800 degreeC in air. It is preferable that content as an inorganic component is 0.1 weight part or more in order to express the addition effect of a layered silicate. Moreover, when it is 20 weight part or less, it is preferable in carrying out the melt molding of the obtained thermoplastic resin composition. From this point, it is more preferable that it is 0.5-12 weight part as an inorganic component, and, as for content of a layered silicate, it is more preferable that it is 1-8 weight part.

The thermoplastic resin used in the present invention is not particularly limited as long as it is a thermoplastic resin capable of melt molding, but is at least one member selected from the group consisting of polyester, polyamide, polyimide, polycarbonate, polyphenylene sulfide, and polyolefin resin. It is preferable. Especially, it is preferable that it is polyester or polycarbonate.

As polyester, the thing which polycondensed dicarboxylic acid and / or its derivative (s) and diol, the thing which consists of hydroxycarboxylic acid, or these copolymers is pointed out. Examples of the dicarboxylic acid component constituting the polyester include terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 2,2'-biphenyldicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 4,4'-diphenylmethanedicarboxylic acid, Aromatic dicarboxylic acids such as 4,4'-diphenylsulfondicarboxylic acid, 4,4'-diphenylisopropyldendicarboxylic acid, 5-sodium sulfoisophthalic acid, oxalic acid, succinic acid, adipic acid Aliphatic dicarboxylic acids such as sebacic acid, dodecanedicarboxylic acid, octadecanedicarboxylic acid, maleic acid and fumaric acid, and cyclic aliphatic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid Can be mentioned. Examples of the diol include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,2-dimethylpropanediol, neopentyl glycol, and 1,5-pentadiol , 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexamethanol, trimethylene Aliphatic diols such as glycol, tetramethylene glycol, pentamethylene glycol, octamethylene glycol, diethylene glycol, dipropylene glycol, hydroquinone, resorcinol, bisphenol A, and 2,2-bis (2'-hydroxyethoxyphenyl And diphenols such as propane. Examples of the hydroxycarboxylic acid include p-hydroxybenzoic acid, p- (hydroxyethoxybenzoic acid, 6-hydroxy-2-naphthoic acid, 7-hydroxy-2-naphthoic acid, 4'-hydroxy-biphenyl Aromatic hydroxycarboxylic acids, such as 4-carboxylic acid, etc. are mentioned.

Specific examples of preferred polyesters include polyethylene terephthalate (PET), polybutylene terephthalate, polycyclohexylenedimethylene terephthalate, polyethylene-2, 6-naphthalate, polybutylene naphthalate, polyethylene isophthalate-tere Phthalate copolymer, p-hydroxybenzoic acid-6-hydroxy-2-naphthoic acid copolymer, and the like.

As polyamide, the thing which polycondensed dicarboxylic acid and / or its derivative, and diamine, what consists of aminocarboxylic acid, or these copolymers is pointed out. Examples of the carboxylic acid component constituting the polyamide include aliphatic dicarboxylic acids such as adipic acid, sebacic acid, dodecanedicarboxylic acid, and octadecanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid. Cyclic aliphatic dicarboxylic acid, terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 4,4 '-Biphenyldicarboxylic acid, 2,2'-biphenyldicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 4,4'-diphenylmethanedicarboxylic acid, 4,4 Aromatic dicarboxylic acids, such as'-diphenyl sulfone dicarboxylic acid, etc. are mentioned. Examples of the diamine include aliphatic diamines such as butanediamine, pentanediamine, hexanediamine, heptanediamine, nonanediamine and dodecanediamine, and aliphatic diamines having a substituent such as trimethyl-1,6-hexanediamine, m-phenylenediamine, and p- Phenylenediamine, 1,4-diaminonaphthalene, 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, 2,6-diaminonaphthalene, 2,7-diaminonaphthalene, 3, 3'-dia Minobiphenyl, 4,4'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3,3'-diaminodiphenylether, 3,4'-diaminodiphenylether, 4,4 ' -Diaminodiphenyl ether, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone , 3,3'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylthioether, 1,3-bis (3-aminophenoxy) benzene , 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy Aromatic diamines such as benzene, 1, 4-bis (4-aminophenoxy) benzene, 1,1-bis (4-aminophenyl) ethane, and 2,2-bis (4-aminophenyl) propane. . These may be used independently but may be used in plurality. Examples of aminocarboxylic acids include aliphatic aminocarboxylic acids such as 6-aminohexanoic acid and 12-aminododecanoic acid, p-aminobenzoic acid, 6-amino-2-naphthoic acid, and 7-amino-2-naphthoic acid. Aromatic aminocarboxylic acid, etc. are mentioned.

Specific examples of preferred polyamides include aliphatic polyamides such as nylon 6,6, nylon 6, nylon 12, semiaromatic polyamides such as polyhexamethylene terephthalamide, polyhexamethylene isophthalamide, copolymers thereof, and the like. can do.

 As a polyimide, the thing which polycondensed tetracarboxylic acid and / or its derivative (s), and diamine, the thing which consists of aminodicarboxylic acid, or these copolymers is pointed out. Examples of the tetracarboxylic acid constituting the polyimide include pyromellitic acid, 1,2,3,4-benzenetetracarboxylic acid, 2,2 ', 3,3'-benzophenonetetracarboxylic acid, and 2,3. ', 3,4'-benzophenonetetracarboxylic acid, 3,3', 4,4'-benzophenonetetracarboxylic acid, 3,3 ', 4,4'-biphenyltetracarboxylic acid, 2, 2 ', 3,3'-biphenyltetracarboxylic acid, 2,3,3', 4'-biphenyltetracarboxylic acid, 1,2,4,5-naphthalenetetracarboxylic acid, 1,2, 5,6-naphthalenetetracarboxylic acid, 1,2,6,7-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid Acid, 3,4,9,10-perylenetetracarboxylic acid, bis (2,3-dicarboxylphenyl) ether, bis (3,4-dicarboxylphenyl) ether, bis (2,3-dica Reboxylphenyl) methane, bis (3,4-dicarboxylphenyl) methane, bis (2,3-dicarboxylphenyl) sulfone, bis (3,4-dicarboxylphenyl) sulfone, 1,1-bis (2,3-dicarboxylphenyl) ethane, 1,1-bis ( 3,4-dicarboxylphenyl) ethane, 2,2-bis (2,3-dicarboxylphenyl) propane, 2,2-bis (3,4-dicarboxylphenyl) propane, 1,1,1 And 3,3,3-hexafluoro-2,2-bis (3,4-dicarboxylphenyl) propane dianhydride, bis (3,4-dicarboxylphenyl) dimethylsilane dianhydride, and the like. have. Examples of the diamine include aliphatic diamines having substituents such as aliphatic diamines such as butanediamine, pentanediamine, hexanediamine, heptanediamine, nonanediamine, and dodecanediamine, isophordiamine, and trimethyl-1,6-hexanediamine. These may be used independently but may be used in plurality. Examples of the aminodicarboxylic acid include aliphatic aminocarboxylic acids such as 6-aminohexanoic acid and 12-aminododecanoic acid.

As a specific example of a preferable polyimide, paradodecamethylene pyromellitimide, paraoundcamethylene pyromellitimide, etc. can be illustrated. Moreover, as a commercial item, a brand name urtem (polyetherimide) etc. can also be illustrated as a preferable thing.

As a polycarbonate, the polycarbonate which consists of various bisphenols can be illustrated. Examples of bisphenols include bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) ethane, and 2,2-bis (4- Hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxyphenyl) heptane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4 -Hydroxy-3,5-dibromophenyl) propane, bis (4-hydroxyphenyl) phenylmethane, 4,4'-dihydroxyphenyl-1,1'-m-diisopropylbenzene, 4, Bis (4-hydroxyallyl) alkanes such as 4'-dihydroxyphenyl-9, 9-fluorene, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4 -Hydroxyphenyl) cyclohexane, 1-methyl-1- (4-hydroxyphenyl) -4- (dimethyl-4-hydroxyphenyl) methyl-cyclohexane, 4- [1- [3- (4-hydroxy Oxyphenyl) -4-methylcyclohexyl] -1-methylethyl] -phenol, 4,4 '-[1-methyl-4- (1-methylethyl) -1,3-cyclohexanediyl] bisphenol, 2, 2,2 ', 2'-tetrahydro-3,3,3', 3'-tetramethyl-1,1'-spirobis- [1H-indene] -6,6 Bis (hydroxyallyl) cycloalkanes such as diol, bis (4-hydroxyphenyl) ether, bis (4-hydroxy-3,5-dichlorophenyl) ether, and 4,4'-dihydroxy Dihydroxyallyl ethers such as 3,3'-dimethylphenyl ether, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxy-3 and 3'-dimethyldiphenyl sulfide Dihydroxy diallyl, such as dihydroxy diallyl sulfide, 4,4'- dihydroxy diphenyl sulfoxide, and 4,4'- dihydroxy-3,3'- dimethyl diphenyl sulfoxide And dihydroxydiallyl sulfones such as sulfoxy, 4,4'-dihydroxydiphenyl sulfone and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone. Among them, polycarbonate using 2,2-bis (4-hydroxyphenyl) propane is preferred in terms of physical properties and cost.

As polyphenylene sulfide, what made the aromatic ring the polymer by sulfide bond, branched or linear polyphenylene sulfide and its copolymer can be illustrated. Specifically, paraphenylene sulfide, metaphenylene sulfide and polymers thereof, ether units copolymerizable with these, sulfone units, biphenyl units, naphthyl units, substituted phenyl sulfide units, trifunctional phenyl sulfide units and the like The copolymer which has a in a molecule | numerator is mentioned. Among these, paraphenylene sulfide is preferable.

Examples of the polyolefin resin include non-alicyclic polyolefins such as polyethylene, polypropylene and poly4-methylpentene-1, norbornene-α olefin copolymers, dicyclopentadiene-α olefin copolymer hydrides, norbornene derivatives or tetra Alicyclic polyolefin resin, such as a ring-opening polymer hydride of a cyclododecene derivative, hydrogenated polystyrene resin, etc. are mentioned. Specifically, for example, norbornene derivatives-alpha olefin copolymers such as TOPAS manufactured by Tiko Corp., APEL manufactured by Mitsui Chemicals, norbornene derivatives such as Nione Xeon manufactured Zeonex, zeonoa, ARTSR manufactured by JSR, or tetracyclodode The ring-opened polymer hydride of a sen derivative can be illustrated.

The resin composition of the present invention is characterized in that the average number of layers of the layered silicate in the thermoplastic resin is 2 to 8 layers. The average number of layers of the layered silicate is calculated by using the scattering angle and the half width of the scattering peak resulting from the interlayer scattering of the layered silicate, and the interlayer distance and the layer thickness are calculated by X-ray scattering. It can be obtained by dividing by.

As a method of calculating the layer thickness from the half width, Scherrer's equation of the following formula (3) is used.

D = K.λ / βcosθ (3)

D = size of the determinant

λ: measured X-ray wavelength

β: half width

θ: Bragg angle of diffraction line

K: Scherrer Integer

When the layered silicate is peeled off to a single layer, it is not detected by this method. However, in the resin composition, if the average number of layers can be confirmed to be 2 to 8 layers, it is sufficient for the purposes of the present invention. As long as the formability of the composition, in particular, fluidity is not impaired, a single layer may be included in the composition. However, in general, the thinner the layer thickness, the lower the elastic modulus of bending, so that the resin composition of the present invention is peeled off in a single layer. One layered silicate is preferably 50% or less, more preferably 30% or less, based on the total amount of monolayers of the layered silicate. This quantity can be estimated using a transmission electron microscope to obtain an average yield ratio. When the average number of layers is small, as described above, the thinner the layer thickness, the lower the elastic modulus of bending. On the other hand, when the average number of layers exceeds eight layers, the dispersion of the layered silicate is insufficient, and the effect of improving physical properties is reduced by dispersing the layered silicate. As average number of layers, 3-7 layers are more preferable, 3.5-6 layers are more preferable, and 4-5 layers are more preferable.

The resin composition of this invention can be manufactured by mixing the layered silicate ion-exchanged with said organic onium ion to a thermoplastic resin. As a method of mixing the layered silicate with the thermoplastic resin, a method of melt kneading the layered silicate together with the thermoplastic resin using a single screw or twin screw extruder, together with the raw material of the thermoplastic resin or the polymerization solvent in the polymerization reaction of the thermoplastic resin The method etc. which disperse | distribute layered silicate and obtain a composition can be illustrated. In any method, it is possible to obtain a good dispersion, but in order to make the heat history of the ion-exchanged layer silicate as small as possible, a method of melt kneading the layered silicate with the thermoplastic resin is preferable. As a method of melt-kneading, for example, powder or granules of thermoplastic resin and layered silicate are mixed in advance, and melt-kneaded at once, or layered silicate using a facility such as a side feeder with respect to the melted thermoplastic resin. The method of melt-kneading by adding this etc. is mentioned.

In melt kneading, the shear rate is preferably 250 / s or more. Shear rate is calculated | required by following formula (4).

γ = πd (N / 60) / C (4)

(γ: shear rate (/ s), d: screw inner diameter (mm), N: screw rotation speed (rpm), C: screw

Clearance between crew and barrel (mm))

As such melt kneading, a conventionally known method can be used, and for example, an extruder such as a single screw extruder or a twin screw extruder can be used. If the shear rate at that time is 25O / s or less, it is not preferable because the kneading ability is insufficient and the dispersibility of the layered silicate in the target polyester composition becomes insufficient. More preferably, it is 280 / s or more, More preferably, it is 300 / s or more.

Moreover, as for the temperature at the time of melt-kneading, 350 degreeC or more is preferable for the fluid flow start temperature (glass transition temperature as amorphous resin, melting point as crystalline resin) of polyester, and (flow start temperature +5) degreeC or more and 330 degreeC or less It is more preferable, and (flow start temperature +10) degreeC or more and 320 degrees C or less are further more preferable. If the temperature is too lower than the flow initiation temperature, it is not preferable because melt molding becomes difficult, and if the temperature is higher than 350 ° C., decomposition of the ion-exchanged layered silicate is severe and undesirable.

Thus, by melt-kneading the layered silicate together with the thermoplastic resin using a single screw or twin screw extruder, it is possible to obtain a highly dispersed composition of the layered silicate even in a thermoplastic resin in which the layered silicate is hard to disperse. Therefore, it is possible to use suitably as a use | use_use which surface problem is, for example, various resin materials for shaping | molding, such as a fiber and a film.

The resin composition of this invention can be melt-molded in accordance with a conventionally well-known method. As melt-molding temperature, the flow start temperature (glass transition temperature as amorphous resin, melting point as crystalline resin) more than 350 degreeC is preferable, (flow start temperature +5) degreeC or more and 330 degrees C or less of a thermoplastic resin is more preferable. (Flow start temperature +10) degreeC or more and 320 degrees C or less are more preferable. If the temperature is too lower than the flow start temperature, melt molding may be difficult. If the temperature is higher than 350 ° C, decomposition of the ion-exchanged layered silicate may be severe.

A film can be obtained preferably from the resin composition which consists of the above thermoplastic resin and layered silicate.

The film of this invention has high dispersibility of layered silicate, and is excellent in heat resistance, gas barrier property, flame retardancy, elasticity, and toughness. In order to obtain a film excellent in mechanical strength in this manner, polyester is preferable as the thermoplastic resin constituting the composition and the film, and polyethylene-2 and 6-naphthalate are particularly preferred.

Preferably the thickness of the film obtained by this invention is 3-50 micrometers. In the present invention, a film having high strength can be produced even if it is thin (e.g., having a thickness of 3 to 20 µm) from the high dispersibility of the layered silicate.

When manufacturing a film, it is preferable to melt-mold and extend the resin composition which consists of a thermoplastic resin and a layered silicate. As a extending | stretching method of a film, Preferably, the method of extending | stretching sequentially or simultaneously in the uniaxial or biaxial direction is mentioned. More specifically, the stretching temperature is preferably at least the glass transition point of the resin composition + 90 ° C. or less, more preferably at least the glass transition point of the resin composition + 70 ° C., even more preferably the glass transition point. It is above the glass transition point +60 degreeC. Even if the stretching temperature is too low or too high, it is difficult and undesirable to produce a uniform film. Moreover, as a draw ratio, as surface magnification, Preferably it is 2 times or more and 100 times or less, More preferably, they are 4 times or more and 70 times or less, More preferably, they are 6 times or more and 50 times or less.

In the present invention, when the thermoplastic resin is crystalline, it is preferable to promote and fix the crystallization of the resin composition by heat treatment after the stretching orientation of the film. As temperature of heat processing, more than glass transition point of a resin and below melting point are preferable. More preferable temperature is determined in consideration of the crystallization temperature of the obtained film, the physical properties of the obtained film, and the like.

Effects of the Invention

The ion exchanged layered silicate of the present invention is preferably dispersible in the thermoplastic resin composition. Moreover, the thermoplastic resin composition of this invention is high in the dispersibility of layered silicate, excellent in heat resistance, gas barrier property, flame retardancy, elasticity, toughness, etc., and can be used as various molded objects, a fiber, a film.

The present invention will be described in detail by way of examples below. However, the present invention is not limited to these Examples at all.

(1) layered silicate:

Montmorillonite (Kunimine Industrial Co., Ltd. Kunipia (sodium exchange capacity 109 meqv / 100g)) was used. The interlayer distance was 12.6 kPa.

Fluoromica F (sodium exchange capacity 120 meqv / 100g manufactured by Corp Chemical Co., Ltd.) was used. The interlayer distance was 9.8 kPa.

(2) Cation exchange rate: Using the differential thermal balance TG 8120 by Rigaku Corporation, it calculated | required using the following formula from the weight reduction rate at the time of heating from 20 degreeC / min to 800 degreeC in air atmosphere.

It was calculated | required using the following formula from the weight reduction rate when heating from 20 degreeC / min to 800 degreeC in air atmosphere using the differential thermal balance TG 8120 made from Rigag.

Cation exchange rate (%) = (Wf / (1-Wf)} / (Morg / Msi) × 100 (2)

(Wf is the weight reduction rate by differential thermal balance of layered silicate measured from 120 ° C to 800 ° C at a heating rate of 20 ° C / min, Morg is the molecular weight of the phosphonium ion, Msi is 1 in the cation portion of the layered silicate) The molecular weight per charge in the cation portion of the layered silicate is the value calculated from the inverse of the cation exchange capacity (unit: eq / g) of the layered silicate.

(3) the weight ratio of the thermoplastic resin and the inorganic component of the layered silicate in the resin composition:

It calculated | required from the weight reduction rate at the time of heating to 800 degreeC at 20 degreeC / min in air atmosphere using the differential thermal balance TG 8120 by Rigaku Corporation.

(4) Pyrolysis temperature: Using the differential thermal balance TG 8120 by Rigaku Co., Ltd., the temperature which reduced 5 weight% weight when heated to 800 degreeC at 20 degreeC / min in nitrogen was calculated | required.

(5) Interlayer distance and average number of layers of layered silicate: It calculated from the diffraction peak position using the powder X-ray diffraction apparatus RAD-B by Rigaku Corporation. In addition, the Scherrer constant was calculated as 0.9.

(6) Reducing viscosity (ηsp / C): The reducing viscosity was measured at a concentration of 1.2 g / dl at 35 ° C. using a solution of phenol / tetrachloroethane (weight ratio 4: 6).

(7) Specific surface area: The specific surface area, QUANTUM CHROME Co., Ltd., and measured using the N ₂ gas in the NOVA 1200, obtained by dividing the weight of the sample.

Reference Example 1 Synthesis of 10-Bromodecamethylenephthalimide

Into the flask, 85 parts by weight of potassium phthalimide, 1008 parts by weight of 1,10-dibromodecane, and 430 parts by weight of dimethylformamide (dehydrated sufficiently) were added to the flask, followed by heating at 10 ° C. for 20 hours. After heating, all volatile components were removed and the residue was extracted with xylene. The volatile components were distilled off from the extracted solution, and the residue was left at room temperature to obtain crystals of 10-bromodecamethylene phthalimide.

Reference Example 2 Synthesis of N-phthalimide decamethylene-2-heptadecylimidazole bromide

20 parts by weight of 2-heptadecylimidazole and 24 parts by weight of phthalimide decamethylene imidazolinium bromide obtained in Reference Example 1 were stirred and reacted by stirring at about 100 ° C. for 8 to 10 hours to form N-phthalimide decamethylene-. 2-heptadecylimidazole bromide was obtained (following formula).

Reference Example 3: Synthesis of N-phthalimide decamethylene-trioctylphosphonium bromide

20 parts by weight of trioctylphosphine and 20 parts by weight of phthalimide decamethylene imidazolinium bromide obtained in Reference Example 1 were added to the flask, followed by stirring at about 100 ° C. for 8-10 h to react with N-phthalimide decamethylene. Trioctylphosphonium bromide was obtained (following formula).

Example 1 Synthesis of Cation Exchanged Layered Silicates

Kunipia F0000 parts by weight and 3000 parts by weight of water were put into the flask, followed by heating and stirring at 80 占 폚. Nippon Chemical manufacture PX 416 here (formula below)

The solution which melt | dissolved 83 weight part in 300 weight part of water was added, and also it stirred at 80 degreeC for 3 hours. The solid was separated from the mixture by filtration, washed three times with methanol and three times with water, and then freeze-dried to obtain a cation exchanged layered silicate. The ion exchange rate was 92%. The specific surface area of the layered silicate obtained in this way was 5.5 m 2 / g. The results of Example 1 are shown in Table 1 below.

Example 2

In addition, 20 parts by weight of the cation-exchanged layered silicate obtained in Example 1 was dispersed in 400 parts by weight of benzene, and freeze drying was performed. The specific surface area of the layered silicate thus obtained was 8.9 m 2 / g. The results of Example 2 are shown in Table 1 below.

Example 3

Into the flask, Kunipia F 100 parts by weight, water 3000 parts by weight, and 500 parts by weight of methanol were added, followed by heating and stirring at 80 ° C. The solution which melt | dissolved 11 weight part of N-phthalimide decamethylene 2-heptadecyl imidazol bromide obtained by the reference example 2 in 300 weight part of methanol was added here, and also it stirred at 80 degreeC for 3 hours. The solid was separated from the mixture by filtration, washed three times with methanol and three times with water, and then freeze-dried to obtain a cation exchanged layered silicate. The ion exchange rate was 68%. The specific surface area of the layered silicate obtained in this way was 5.3 m 2 / g. The results of Example 3 are shown in Table 1 below.

Example 1 Example 2  Example 3 Formula

Left

Ion exchange rate (%) 92 92 68 Specific surface area ㎡ / g 5.5 8.9 5.3 Pyrolysis temperature ℃ 375 Left 370 Interlayer distance Nm 2.3 Left 2.4

Example 4

Into the flask, Kunipia F 100 parts by weight, water 3000 parts by weight, and 500 parts by weight of methanol were added, followed by heating and stirring at 80 ° C. The solution which melt | dissolved 120 weight part of N-phthalimide decamethylene-trioctyl phosphonium bromide obtained by the reference example 3 with 300 weight part of methanol was added here, and also it stirred at 80 degreeC for 3 hours. The solid was separated from the mixture by filtration, washed three times with methanol and three times with water, and then freeze-dried to obtain a cation exchanged layered silicate. The ion exchange rate was 65%. The specific surface area of the layered silicate thus obtained was 5.5 m 2 / g. The results of Example 4 are shown in Table 2 below.

Example 5

Further, 20 parts by weight of the cation-exchanged layered silicate obtained in Example 4 was dispersed with 400 parts by weight of cyclohexane, and freeze-dried. The specific surface area of the layered silicate obtained in this way was 8.3 m 2 / g. The results of Example 5 are shown in Table 2 below.

Example 6

100 parts by weight of Fluoromica F (Coff Chemical Co., Ltd.) and 3000 parts by weight of water were heated and stirred at 80 ° C in a flask. The solution which melt | dissolved 92 weight part of Nippon Chemical make PX416 by 300 weight part of water was added here, and also it stirred at 80 degreeC for 3 hours. The solid was separated from the mixture by filtration, washed three times with methanol and three times with water, and then freeze-dried to obtain a cation exchanged layered silicate. The ion exchange rate was 90%. The specific surface area of the layered silicate obtained in this way was 5.9 m 2 / g. The results of Example 6 are shown in Table 2 below.

Example 4 Example 5 Example 6 Formula

Left

Ion exchange rate (%) 65 65 90 Specific surface area ㎡ / g 5.5 8.3 5.9 Pyrolysis temperature ℃ 374 Left 378 Interlayer distance Nm 2.5 Left 2.4

Example 7 Preparation of Resin Composition

The pellet of poly (ethylene naphthalate) (reduced viscosity is 0.78) and the layered silicate obtained in Example 1 were extruded using a bidirectional twin screw kneading extruder (manufactured by Toyosei Co., Ltd., Labofurast Mill 2D25S), screw After kneading under conditions of a rotational speed of 150 rpm, the pellets were discharged to obtain strand-like pellets of the polyester resin composition after water cooling. The result of the resin composition obtained at this time is shown in following Table 3. Moreover, the resin composition was observed with the transmission electron microscope (FIG. 1). As shown in this figure, the dispersion state of layered silicate was very high. In addition, the layer of layered silicate was peeled off.

Examples 8-12

The resin composition was obtained by the same method except having changed the layered silicate into the layered silicate obtained in Examples 2-6, respectively. The results are shown in Tables 3 and 4.

Example 13

The pellet of polycarbonate (Teijin Kasei Co., Ltd. L1250) and the layered silicate obtained in Example 6 were subjected to ZSK-25 (WERNER & PFLEIDERER) using ZSK-25 (WERNER & PFLEIDERER) extrusion temperature of 280 ° C, screw rotational speed of 280rpm, extrusion speed of 10kg / hour, shear rate After kneading under the condition of 1800 / sec, the mixture was discharged to obtain strand-like pellets of the polyester resin composition after water cooling. The result of the resin composition obtained at this time is shown in following Table 4.

Example 7 Example 8 Example 9 Example 10 Fat Poly (ethylene naphthalate) Poly (ethylene naphthalate) Poly (ethylene naphthalate) Poly (ethylene naphthalate) Reduced viscosity ηsp / C 0.64 0.63 0.62 0.64 Layered silicate Example 1 Example 2 Example 3 Example 4 Inorganic content % 2% 2 2 2 Melting point ℃ 267 268 270 270 Interlayer distance Nm 2.7 2.7 2.5 2.3 Average floors - 4.3 4.4 4.7 4.5

Example 11 Example 12 Example 13 Fat Poly (ethylene naphthalate) Poly (ethylene naphthalate) Poly (ethylene naphthalate) Reduced viscosity ηsp / C 0.64 0.63 0.60 Layered silicate Example 5 Example 6 Example 6 Inorganic content % 2 2 2 Melting point ℃ 269 267 124 Interlayer distance Nm 2.5 2.7 2.3 Average floors - 4.3 4.2 4.9

Example 14, 15: Preparation of film

The strand chips obtained in Example 1 were dried at 170 ° C. for 5 hours, then fed into an extruder hopper, melted at a melting temperature of 300 ° C., and extruded onto a rotary cooling drum at a surface temperature of 80 ° C. through a 1.3 mm slit die. And the unstretched film was obtained. The unstretched film thus obtained was continuously stretched at a temperature of 150 ° C. at MD × TD = 3.0 × 3.0 times and 4.0 × 4.0 times to obtain a biaxially stretched film having a thickness of 15 μm. Furthermore, the obtained biaxially stretched film was heat-fixed at 205 degreeC for 1 minute, and the polyethylene naphthalate / layered silicate composite film was obtained. The Young's modulus of the obtained film was 7.1 GPa and 8.7 GPa in MD direction, respectively.

Comparative Example 1

A layered silicate was obtained in the same manner as in Example 1 except that the freeze drying was changed to vacuum drying at 150 ° C. It was 1.7Om <2> / g when this specific surface area was measured.

Comparative Example 2

The pellet of poly (ethylene naphthalate) (reduced viscosity is 0.78) and the layered silicate obtained in Comparative Example 1 were subjected to an extrusion temperature of 280 ° C using a bidirectional twin screw kneading extruder (manufactured by Toyosei Co., Ltd., Labofurast Mill 2D25S). After kneading under the condition of a screw rotation speed of 150 rpm, the pellets were discharged and water-cooled to obtain strand-like pellets of the polyester resin composition. The obtained pellets were observed with a transmission electron microscope (FIG. 2). The dispersibility of the layered silicate also decreased.

Claims (9)

A layered silicate characterized in that the organic onium ion is ion exchanged by 50 to 100% relative to the ion exchange capacity, and the specific surface area is 2.5 to 100 m 2 / g. The method of claim 1, Organic onium ions are represented by the following formula (1)

(In formula, R <_1> , R <_2> , R <_3> and R <_4> are respectively independently a hydrocarbon group containing a C1-C30 hydrocarbon group or hetero atom, and M is a nitrogen atom or a person atom. Arbitrary R ₁ , R ₂ , R ₃ and R ₄ may form a ring), a layered silicate, characterized in that the organic onium ion. The method of claim 2. The organic onium ion of the formula (1) is M is a phosphonium ion as a person, or M is a nitrogen atom, and any R ₁ , R ₂ , R ₃ and R ₄ Layered silicate, characterized in that it forms a hetero ring and is a heteroaromatic ion. The layered silicate exchanged with the organic onium ion according to any one of claims 1 to 3 is lyophilized using a medium having a melting point of -20 ° C or more and less than 100 ° C. The method of claim 4, wherein A method for producing a layered silicate, wherein the medium having a melting point of from -20 ° C to less than 100 ° C is a nutrient medium of the layered silicate. A resin composition composed of a thermoplastic resin and the layered silicate according to any one of claims 1 to 3, wherein the content of the layered silicate is 0.01 to 20 parts by weight as inorganic ash based on 100 parts by weight of the thermoplastic resin, The average number of layers of the layered silicate is 2 to 8 layers. The manufacturing method of the resin composition by melt-kneading the layered silicate of Claim 6 with a thermoplastic resin using a single screw or twin screw extruder. The method of claim 6, The resin composition whose thermoplastic resin is at least 1 sort (s) chosen from the group which consists of polyester, polyamide, polyimide, polycarbonate, polyphenylene sulfide, and polyolefin resin. The film which consists of a resin composition of Claim 6.

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